Grafting of Poly(methyl methacrylate) Brushes from Magnetite Nanoparticles Using a Phosphonic Acid Based Initiator by Ambient Temperature Atom Transfer Radical Polymerization (ATATRP)

Poly(methyl methacrylate) in the brush form is grown from the surface of magnetite nanoparticles by ambient temperature atom transfer radical polymerization (ATATRP) using a phosphonic acid based initiator. The surface initiator was prepared by the reaction of ethylene glycol with 2-bromoisobutyrl bromide, followed by the reaction with phosphorus oxychloride and hydrolysis. This initiator is anchored to magnetite nanoparticles via physisorption. The ATATRP of methyl methacrylate was carried out in the presence of CuBr/PMDETA complex, without a sacrificial initiator, and the grafting density is found to be as high as 0.90 molecules/nm2. The organic–inorganic hybrid material thus prepared shows exceptional stability in organic solvents unlike unfunctionalized magnetite nanoparticles which tend to flocculate. The polymer brushes of various number average molecular weights were prepared and the molecular weight was determined using size exclusion chromatography, after degrafting the polymer from the magnetite core. Thermogravimetric analysis, X-ray photoelectron spectra and diffused reflection FT-IR were used to confirm the grafting reaction.

[1]  B. Bhushan,et al.  Alkylphosphonate modified aluminum oxide surfaces. , 2006, The journal of physical chemistry. B.

[2]  H. Otsuka,et al.  Polystyrene-Grafted Magnetite Nanoparticles Prepared through Surface-Initiated Nitroxyl-Mediated Radical Polymerization , 2003 .

[3]  J. Rühe,et al.  Synthesis of Poly(styrene) Monolayers Attached to High Surface Area Silica Gels through Self-Assembled Monolayers of Azo Initiators , 1998 .

[4]  Jeremiah A. Johnson,et al.  Toward the Syntheses of Universal Ligands for Metal Oxide Surfaces: Controlling Surface Functionality through Click Chemistry , 2006 .

[5]  Interparticle interaction and size effect in polymer coated magnetite nanoparticles , 2006, cond-mat/0604119.

[6]  N. Zydowicz,et al.  Nitroxide-Mediated Polymerization of Styrene Initiated from the Surface of Silica Nanoparticles. In Situ Generation and Grafting of Alkoxyamine Initiators , 2005 .

[7]  Yu Zhang,et al.  Starch-Coated Superparamagnetic Nanoparticles as MR Contrast Agents , 2003 .

[8]  Howard Katz,et al.  Inorganic oxide core, polymer shell nanocomposite as a high K gate dielectric for flexible electronics applications. , 2005, Journal of the American Chemical Society.

[9]  J. Rühe,et al.  Controlled Growth of PMMA Brushes on Silicon Surfaces at Room Temperature , 2002 .

[10]  D. Leslie-Pelecky,et al.  Iron oxide nanoparticles for sustained delivery of anticancer agents. , 2005, Molecular pharmaceutics.

[11]  K. Matyjaszewski,et al.  Atom transfer radical polymerization. , 2001, Chemical reviews.

[12]  J. Schwartz,et al.  Surface modification of Y2O3 nanoparticles. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[13]  Z John Zhang,et al.  Atom transfer radical polymerization synthesis and magnetic characterization of MnFe2O4/polystyrene core/shell nanoparticles. , 2002, Journal of the American Chemical Society.

[14]  Changwen Hu,et al.  Convenient synthesis of single crystalline magnetic Fe3O4 nanorods , 2003 .

[15]  H. Otsuka,et al.  Polystyrene- and poly(3-vinylpyridine)-grafted magnetite nanoparticles prepared through surface-initiated nitroxide-mediated radical polymerization , 2004 .

[16]  Bing Xu,et al.  Dopamine as a robust anchor to immobilize functional molecules on the iron oxide shell of magnetic nanoparticles. , 2004, Journal of the American Chemical Society.

[17]  Michael Todd,et al.  Synthesis, characterisation and application of silica-magnetite nanocomposites , 2004 .

[18]  B. Sumerlin,et al.  Facile preparation of transition metal nanoparticles stabilized by well-defined (co)polymers synthesized via aqueous reversible addition-fragmentation chain transfer polymerization. , 2002, Journal of the American Chemical Society.

[19]  Zhichuan J. Xu,et al.  Highly ordered self-assembly with large area of Fe3O4 nanoparticles and the magnetic properties. , 2005, The journal of physical chemistry. B.

[20]  A. Fadeev,et al.  Hydrolytic stability of organic monolayers supported on TiO2 and ZrO2. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[21]  A. Fadeev,et al.  Calorimetric study of the reactions of n-alkylphosphonic acids with metal oxide surfaces. , 2005, Journal of colloid and interface science.

[22]  J. Oberdisse,et al.  Surface−Atom Transfer Radical Polymerization from Silica Nanoparticles with Controlled Colloidal Stability , 2004 .

[23]  Marcus Textor,et al.  Alkyl Phosphate Monolayers, Self-Assembled from Aqueous Solution onto Metal Oxide Surfaces , 2001 .

[24]  J. Greneche,et al.  Phosphate Adsorption Properties of Magnetite-Based Nanoparticles , 2007 .

[25]  I. Mondragon,et al.  Functionalization of iron oxide magnetic nanoparticles with poly(methyl methacrylate) brushes via grafting‐from atom transfer radical polymerization , 2007 .

[26]  H. Gu,et al.  Magnetite ferrofluid with high specific absorption rate for application in hyperthermia , 2007 .

[27]  B. Benicewicz,et al.  Synthesis of well-defined polymer brushes grafted onto silica nanoparticles via surface reversible addition-fragmentation chain transfer polymerization , 2005 .

[28]  T. Patten,et al.  Atom transfer radical polymerization from nanoparticles: a tool for the preparation of well-defined hybrid nanostructures and for understanding the chemistry of controlled/"living" radical polymerizations from surfaces. , 2001, Journal of the American Chemical Society.

[29]  Miguel A. Correa-Duarte,et al.  Control of Packing Order of Self-Assembled Monolayers of Magnetite Nanoparticles with and without SiO2 Coating by Microwave Irradiation , 1998 .

[30]  C. Tanford Macromolecules , 1994, Nature.

[31]  K. Koh,et al.  Synthesis of Monodisperse Silica Particles Coated with Well-Defined, High-Density Polymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization , 2005 .

[32]  J. Yarger,et al.  NMR Characterization of Phosphonic Acid Capped SnO2 Nanoparticles , 2007 .